AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

................................2 Working with the coulometric KF instruments ..7 2..........................................21 3........2 The minimum and maximum dosing rate .............1 Titration stand ....................................26 4.......................................4 Control parameters in the volumetric KF titration ......................................................6 General recommendations .................1 Volumetric KF reagents.............................19 3.........4 Polarization current and end point....................................................................29 4.............1 Filling the coulometric cell .............21 3......................35 4.....................11 2.............1.............................2 Stoichiometry of the coulometric KF rection ................................................................2 End point and polarization current.........4 Generator electrode without diaphragm .............................................................19 3.................1 KF coulometry .4 1...................2...3 Concentration determination with Water Standard 10..........................................................................28 4............................3 Secure draining and filling of the titration cell: SOLVENT MANAGER.....................................33 4.......2 The drift ..................3..5 Control paramaters in the coulometric KF Analysis ...............2.......................................................................................................................2.......................................................................13 3..........33 4..........26 4............................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ...4 Cleaning the coulometric KF titration cell........3.......................................8 2..........1 Indication ...............3.......32 4.........1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration .........2 Concentration determination with di-sodium tartrate dihydrate............................................................................................................................38 5 Sampling ....................2 Two-component KF reagent ......................................................................................................7 2................................1 One-component KF reagent .....................33 4.......................................................................13 3..................36 4..................34 4..........................8 2...........................................................1.6 Dissolving capacity of the solvent ...24 4........3......5 1.........................5 Limitations for the use of the cell without diaphragm............................................4.............................................................................................................................................................................6 Termination parameters for both coulometric and volumetric KF titration......3 Pyridine-containing reagents .............4 Concentration determination with pure water..................1........1.......9 2....................26 4..........3 Stirring speed and dispersion of the volumetric KF titrant..................28 4................19 3.........................................1..............6 2 Volumetric and Coulometric Karl Fischer Analyses ... The Karl Fischer titration.....18 3..............................2...1 Principle of bipotentiometric indication ............................................5 Cleaning the measuring electrode .........14 3..................20 3...18 3..........................27 4......5 The solvent..............................3.................................1.....................2...4.......4........................................1..................................................................3 Consequences for practical applications...............................................................3...............................1 How often should the concentration be determined?.......4 1.........1 The influence of atmospheric humidity (drift determination) ...........39 1 ......................2 The Karl Fischer chemical reaction ...............................................10 2...................12 3 Titration control and end point determination....13 3.......................................................................................3 The Cautious start .............................4.......3 Volumetric KF Titration: Titrant concentration.................0 mg/g ...........22 3.....................4................................................8 2...........................................................................11 2..........................................2 Coulometric KF analysis..........................16 3.................1 The Control Band .....................37 4.......................................2.....2...................5 Karl Fischer reagents with ethanol ..........................................2......................................................4.................2 Reaction rate .....................................................................9 2.................1.........9 2...................................1.........................................2........................................7 2.....................................6.............................16 3....29 4....................................3 Iodine generation............2.........................................................................................................4 Special reagents for aldehydes and ketones..........................1 An historic overview .2 When do you have to replace the electrolyte? .......................5 Application tips .

................2 Storing the sample ...........................4 Technical products .......................71 9......................................................................4.............6.............................................................................85 11...................................................40 6 Sample addition ..........................1 Organic Chemicals........1 Solids: Characteristics.......................2 Volumetric Karl Fischer Titration .....................................................................3 Procedure...........1 Reaction with methanol..............................................................................43 6..5 Accessories for sample input ...............................87 11.....................................................87 11...............77 11........................................................................................67 8................................6........4 Liquids: Sample input...............................................................4 Manual Karl Fischer drying oven........................................................................................................................................................................................49 7............................................2 Solid samples................................4............................71 9.....4 Lyophilized substance in septum bottles................................43 6.........................................2 Liquid samples ..................................................................................................1 Taking the sample.........................................88 11.................................................................................70 9..................................1 Liquid samples ...........2 Purge gas...2 External extraction ...........................................................48 7....3 Technical products – organic .............3...............1...............73 10.......................................................6.............................................................1 Coulometry.........................................70 9..............................................5 Additional literature ....55 7...80 11........................................58 7...................70 9.........3 Amount of sample .......2..............................................................................................................................6 Determination using the drying oven ......1 Effects of temperature.................................................................1 Volumetric methods ...................................................................................2 Reaction with water.........................................57 7....................................6.....................................................47 7..........................3..............................4...............................6.............................5 STROMBOLI automatic oven sample changer ..............................2 Foods and technical products .........................................................................................................................................................................................................................................................................................................................2 Measurement accuracy..............................................................................67 8..................2........3 Reaction with iodine ...............................4 Example: reevaluation of side reactions ........................................................39 5........................1........................2 Inorganic chemicals ................................5 Determination of water in gases ....................................................................6 References......86 11..39 5.....................83 11...........75 11 Karl Fischer Titration: The Method at a Glance ................................................................79 11...................................67 8...................86 11..................................2.....................................................................1 Resolution and detection limit ........1...........59 7...................1 Solid samples........................................................................................................................................................................2 Side reactions .....................58 7....1............................6 Food ....................................................................68 9 Interferences ..................................................................................................................................72 10 Troubleshooting .....................................................................71 9...................................79 11.........................................................................................................................2 Coulometric methods ................................................................................................80 11.......1 Principle ......................................................................................................................................73 10.........................4.............................................................................................................................3 Titration Methods .....................79 11....................77 11..............................87 11......3 External dissolution .................78 11.......................................62 8 Measurement results .......................78 11......................................................................................1 Internal extraction .............................58 7...........................86 11....4 Sample preparation and input .....................................................................................................................................................................1 Organic and inorganic chemicals .................60 7.........................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.............1.....................................................................................................................4.....77 11.2 Solids: Sample input ..............................................................3 Repeatability ...........89 12 Appendix ................5 Technical natural products ...............................................54 7....81 11.....................inorganic ...........1.................................83 11....................................3 Liquids: Characteristics ...........2.................................4..90 2 .............................................45 7 Release of water from the sample ..

..................................1 Formula for the external extraction ....................96 12...........................6.........................2 For samples poorly soluble in methanol or ethanol...............................................3 Standards for Karl Fischer coulometry........98 13..5 For acids and bases (pH value) ............................3 For samples insoluble in methanol or ethanol.........95 12.....98 13................4....................3 For samples that are insoluble in methanol or ethanol ....98 3 ......................................3 Reagents for coulometry: .4 Reagents and solvents for coulometric analysis ................6...............................................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.....1 For samples that are soluble in methanol or ethanol ..........4 For ketones and aldehydes......................91 12.......................................6..........................................4................................................5 For acids and bases (pH value) ...............4 For ketones and aldehydes..95 12........................................................................................................................5 Water Standards for Karl Fischer volumetric titration..2 Two-component reagent: .............................................................6........98 13................................96 12...............97 13 Hazards and waste disposal tips ..93 12.........................92 12........................................2 For samples that are poorely soluble in methanol or ethanol ......................................................2 Formula for the external dissolution ..............................90 12........92 12..........................6...........................4................98 13....4 Safety data for the KF-components and auxiliary solvents: .................................4..............91 12............92 12.................4...............95 12..................1 For samples soluble in methanol or ethanol .....................................6 Titrants and solvents for volumetric analysis .........................................95 12...............................................................................1 One-component reagent ......................................94 12...........................93 12.................................................................................

Publication: Coulometric Karl Fischer Titration by A. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. by G. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . DL37 KF Coulometer from METTLER TOLEDO. They replaced the DL18/35 KF Volumetric Titrators. April 1956. Publication on stabilized single-component Karl Fischer reagent by E. promoted by publications by E.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration.Direct method”). First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. M.J. Wernimont and F. First diaphragm-less cell for coulometric KF titration. Publication: “The Dead-Stop End Point“. Jungnickel. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination.0.1 mg/g) with test certificate according to DIN 50049-2. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available.0. First coulometric KF titration instruments are commercially available. First German DIN standard for the Karl Fischer titration (DIN 51777. Improved METTLER TOLEDO DO307 KF Manual Drying Oven.5% and 1%. Eberius [3]. 1. D. Solid KF Oven Standards with water contents of 5. L. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Hopkinson [2]. 2000 2001 2002 2008 4 . Peters and J. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. S. and solvent dispensing and removal. Meyer and C.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Enormous spread of the use of KF titration.Boyd [4]. respectively. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Automatic KF titration instruments with piston motorized burettes. Pyridine-free KF reagents are commercially available. 0. Introduction of less poisonous KF reagents based on ethanolic solution. Use of Karl Fischer method spreads. titrant specific standard parameters and LEARN titration. Water standards (10. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer.

the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. it is necessary to neutralize the acids that are formed during the process (HI and H2SO4).5.5 to 8. In an alcohol-free solution. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. all the sulfur dioxide is present as methyl sulfite. Verhoff and E. Bryanz and Mitchell [6] formulated a two-step reaction: 1..METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. methanol not only acts as a solvent but also participates directly in the reaction itself. the maximum reaction rate is reached here and cannot increase further. I2 + SO2 + 3 Py + H2O → 2. Karl Fischer used pyridine for this purpose. the more methyl sulfite is formed by the capture of protons. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. the 5 . but rather the methyl sulfite ion. In the pH range 5. the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. In an alcoholic solution. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. it only acts as a buffering agent and can therefore be replaced by other bases. i. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1]. The rate of the Karl Fischer reaction. I2 + SO2 + 3 Py + H2O → 2. W. and the faster the rate of the Karl Fischer reaction. Methanol proved to be suitable as a solvent. C.e. In order to achieve an equilibrium shift to the right. At pH values above 8. Smith. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. described by the rate constant k.

Verhoff and E.C.3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5. however. in a titration. diethylene glycol monoethylether) [10. If a methanol-free titrant has to be used (e.g. methanol) (e. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. methoxyethanol. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. This reagent not only replaced the toxic. and references therein]. This improves the titer stability.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. this results in a more sluggish endpoint and higher iodine consumption. ethanol. for determination in ketones or aldehydes). Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. is not a serious limitation because the water concentration in the solvent is usually much less. Methanol should therefore always be present in the minimum required amount. On the basis of this knowledge. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. This. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L.g.g. In 1988. for instance. ROH + SO2 + RN 2. A. and for bases: salicylic acid). With acidic or basic samples. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. you can use other alkohols such as. J. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e.5 to 8. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. E. 2-propanol. ethylene glycol monomethyl ether. pungent pyridine. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. Studies by E. pH values less than 4 and greater than 8 should be avoided in practice. Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction.g. 6 .

where a solution containing iodine is added using a motorized piston burette.5 mg/mL per year in a sealed bottle.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. is approximately 0. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration. The reagent can be stored for approximately two years. i.100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%. The drop in titer. Coulometric Karl Fischer Analysis. Suitable for samples where water is present as a major component: 100 ppm . Suitable for samples where water is present in trace amounts: 1 ppm . You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. 1 mg/mL for samples with a water content of less than 200 ppm. dissolved in a suitable alcohol.1. 2 mg/mL for samples with a water content of less than 1000 ppm..5% 2. the decrease in concentration.e. 7 .1 Volumetric KF reagents 2. sulfur dioxide and imidazole.1 One-component KF reagent The titrant contains iodine. The solvent is methanol.

pyridine. One-component reagent: The titrant contains iodine. from VWR/MERCK) are commercially available to prevent this problem. sulfur dioxide and 2-methoxyethanol. These solutions are mixed 1:1 just before use to form the one-component titrant. sulfur dioxide and pyridine. stable titer. methanol. 8 . Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. A titration speed two or three times as high can be achieved with the two-component reagent. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. imidazole. The titrant has a stable titer. 2 mg/mL for samples with a water content of less than 1000 ppm. To improve stability.g. Special methanol-free KF one-component reagents such as e. Solvent capacity restricted. such as amines. Note that it may be necessary to adapt the end point value in the titration method to these reagents. + Simple handling.g.g. e. increases their lifetime. dissolved in methanol. provided that the bottle is tightly sealed. whereas the solvent contains 2-chloroethanol and trichloromethane.2 Two-component KF reagent The titrant contains iodine and methanol. favorably priced. HYDRANAL® (Composite 5K and Working Medium K. which allow for fast and accurate Karl Fischer titrations. One-component reagent: The titrant contains iodine. – Titer less stable. Reagents One-component Two-component 2.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. Two-component reagent: The titrant contains iodine dissolved in an alcohol. The titration takes slightly longer than with the standard KF reagent. imidazole. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. additional water is produced and titrated at the same time.g. methanol) and B (iodine.4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. reagents containing pyridine are still used because they are cheaper and can be made in-house.1. This special reagent is also suitable for substances that react with methanol. The solvent contains sulfur dioxide. from Sigma-Aldrich) and e. leading to higher water contents and a vanishing end point. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. whereas the solvent consists of sulfur dioxide and a base. The separation into titrant and solvent improves stability of the KF reagents. and results in higher titration speed. The solvent is either methanol or consists of methanol mixtures. or an alcoholic mixture. 2. methanol). imidazole and methanol. titration speed slower. This reagent is declared as “rapid”. As a result. dissolved in an alcohol (usually methanol). High titration speed. Both the components are very stable in storage.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.1. e.1.

2 Coulometric KF analysis 2. The classical coulometric cell consists of two parts. the anode compartment and the cathode compartment. however. or “inner burette”) incorporated into the glass titration cell. 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. Both parts are separated by a diaphragm. imidazole. a double pin platinum electrode.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. The generator is close to the measuring electrode*. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry.1. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . 9 . These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol. diethanolamine and ethanol. whereas the solvent contains sulfur dioxide. two-component. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell.2. ethanol-based reagents were launched in 1998. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol. The titrant contains iodine and ethanol.

Depending on the application. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. Note that methyl sulfonic acid. present in the anolyte compartment. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. An ammonium salt is added to the catholyte in order to promote hydrogen production. I2. CH3SO3H. iodine reacts with water. 2 I. To calculate it. 1C=1A·1s On the other hand.e. This can cause the cathode to become black. The value 96845 C/mol is known as the Faraday constant.e. imidazole and iodide salts. i. used to generate iodine. To avoid this. This consists of sulfur dioxide. it is necessary to first recall the definition of 1 Coulomb: one coulomb.g. is the quantity of charge that is transported by a current of 1 ampere in one second. The negative iodide ions release electrons at the anode and form iodine. other solvents such e.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. the catholyte should be replaced once in two weeks. i.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. 96485 C of current are needed. C. iodine is generated from iodide by electrochemical oxidation. The cathode compartment contains the catholyte. releasing two electrons at the anode. as chloroform. are oxidized to one molecule of iodine. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). Methanol or ethanol is used as solvent. I-. Cathode reaction At the cathode. hexanol or ethylene glycol may be added. Anode reaction At the anode. octanol. Subsequently.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. 2 [RN]H+ + 2e. The catholyte is either a manufacturer-specific special reagent. 2. In Karl Fischer reaction two iodide ions. C.→ I2 → H2O 10 .2. the positive hydrogen ions are reduced to hydrogen. This is the main product formed. or the same reagent as used in the anode compartment. which subsequently reacts with water. it is known that to produce one mole of a chemical substance that requires one electron.

coulometry is designated as absolute method. 2. hexanol. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. In addition. Since current and time can be accurately measured. the coulometer operates with current pulses of 400 mA. 2. it is used as a reference method for the determination of water content. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10. etc. With standard conductivity values. the maximum possible current applied by the instrument is 100 mA. less than 3–4 μS/cm). the current conversion efficiency for iodine production is assumed to be 100%. As a consequence. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA). Since the molar mass of water is 18. At very low conductivities (i.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore.3 Iodine generation Iodine is generated by means of current pulses of 400.2.015 g/mol. 300. no standardization of the coulometric KF reagents is necessary. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . Nevertheless. 2 x 96485 C/mol is required for 1 mole of water. 200 and 100 mA. For an electrochemically optimized Karl Fischer cell.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard.).712 C electrical current. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer. For this reason.2.e.

lower than 50 μg water/sample). This is a very good reducing agent. However. 12 . especially when easily reducible. a different geometry is used for the generating cell without diaphragm.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. In practice. the relative error due to this effect can be minimized by using a larger amount of sample. Thus. etc. The latter can thus react more efficiently with water. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this.. may also be reduced at the cathode by the formation of water. The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. for measurement of samples having a very low water content (e.ethers ketones (with special reagent) .chlorinated hydrocarbons alcohols . the cathode is a small-size pin). the cell with diaphragm may yield more precise results.2.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons .e. it is still possible for a very small amount of iodine to reach the cathode. Nascent hydrogen is formed at the cathode. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. other easily reducible substances such as unsaturated fatty acids.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced. In addition.phenols (most) esters . 2. To avoid this concurring reaction.acetamides etheric oils and essences . This effect is further enhanced by the small dimensions of the cathode. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface.g. Nevertheless. and for very accurate determinations. especially for nitro compounds such as nitrobenzene. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i.

. The control of the titration is only possible if the end point is indicated. . . When the voltage drops below a defined value.the termination of the analysis. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. there is no free iodine in the titration/anolyte solution.the reaction rate of the Karl Fischer reaction . Ideally. iodine should be added or generated as quickly as possible. and the addition or production stopped exactly at the end point.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry"). 13 .1 Indication 3. The resulting titration speed depends on the following factors: . there will be free iodine in the titration solution. • • As long as the added iodine reacts with the water. the water content.the addition speed or generation rate of iodine . A small. • • • As soon as all the water has reacted with iodine.the control algorithm and its parameters. the titration is terminated.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled.the stirring speed and mixing of the sample solution.the viscosity of the solution and its temperature. Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. and hence. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. 3.1. A high voltage is necessary to maintain the specified polarization current at the electrode.

1. A voltage of ca. This drop in voltage is used to indicate the end of the titration.(to a lesser extent) the type of electrode (i. which are present in excess in the titration solution. This free iodine gives rise to "ionic conduction". Above all. It then acquires two electrons and turns into iodide ions (2 I–). . Ipol . This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction".e. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. i. free iodine is present in the titration/anolyte solution. The iodine is present only at low concentration. respectively. If mixing is poor. I2.METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. 14 . geometry and dimensions of the metal parts) .the polarization current. no iodine reaches the negatively charged platinum pin. where they donate the electrons and form an iodine molecule.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. again. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). The end point value mainly depends on . Iodide ions. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. 3. At the end of the titration: As soon as all the water in the sample has reacted with the iodine.e. this value depends on the polarization current. • • At the beginning and during the titration: As long as the iodine generated reacts with the water.the solvent or anolyte used in the instrument. The two negatively charged iodide ions are attracted by the positively charged platinum pin. there is no free iodine in the titration/anolyte solution.

the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. the polarization current should be set as low as possible. Sensors with a large platinum surface. With used sensors. with longer pins. However. i. Sensors with short platinum pins (< 3 mm). As a consequence. 15 . pin length: 3 . and increases the sensor resistance.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. On the other hand. exhibit a larger potential jump and also a higher end point. a layer is formed on the surface of the platinum pin sensor. Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. With use. The current density can be compared to a water pipe where a specific water has to flow.e. its surface can easily bond suitable chemical compounds. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. The larger the diameter of the pipe. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). e.e. iodine excess should be as low as possible to get accurate results. This makes it more difficult to stop the titration at the right moment. In general the larger the platinum surface the smaller the current density.4 mm. a double ring or plates instead of rings. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). just after the equivalence point. and subsequently it remains constant. i. The layer is formed during the first ten titrations. on the other hand. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. exhibit a smaller potential jump. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal. pin length: 3 to 4 mm. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. and increases the risk of over titration.

[H2O] . If 16 .0 mL 1.and on the iodine concentration. It is consumed with each additional measured sample leading to a decreasing dioxide concentration.the water concentration. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. shape of the vessel (volumetric KF titration).5 . which gives a high reaction rate. the titration may also be too slow. the water concentration is lower. and overtitration may occur. note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant. irregular.the sulfur dioxide concentration.2 min with a titrant consumption of 2. the water content is high. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present. 2. Mixing is influenced by the 1. As a consequence. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. stirring speed. sulfur dioxide is present in large excess in the anolyte. In the volumetric KF titration. Iodine generation or addition is usually the rate determining factor.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. Towards the end of the titration.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. with the twocomponent reagents. lower reaction rates are achieved with anolyte solutions that have been used for a long time. [SO2] . a large excess of sulfur dioxide is present in the solvent. 3.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: .3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. On the other hand. If the speed is too slow. point of titrant addition (volumetric KF titration). Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. At the beginning. [I2] .0 mL In the coulometric KF analysis. 3.

but rather along the base directly towards the sensor. the stirring speed is too fast.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. If a longer stirring bar is used. leading to slower addition and longer titration time. Furthermore. Bubbles falsify the measured values. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. This is essential for a fast reaction rate and for short titration times. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. Otherwise the sensor may directly detect added iodine. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. turbulence is not achieved and the mixing effectiveness is lower. Iodine would not be distributed upwards. 17 .

1 The Control Band The control band is a modifiable control parameter for both types of KF reagents.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. The dynamic behaviour of the control can be influenced by a variation of the control band.4. The following drawing reveals a schematical illustration of the control band: 18 .4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters.

You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt.e. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value.g. however. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control. if the polarization current changes.4. the titration will take too long. This is more suited for small water amounts. if the control band width is decreased.4.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants. Recommendations 1.4 Polarization current and end point Each end point is valid for a specific polarization current. the titration starts so quickly that overtitration may occur. In particular. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up. at higher water contents. the titrator automatically issues a warning. the control reacts more sensitively to potential changes.4. i. In the cautious mode. sensors with very short platinum pins (< 3 mm). Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. With large amounts of water. The maximum dosing rate is dependent on the actual burette size. The following points represent possible contributing factors: contaminated or old sensors. The end point for a specific polarization current is influenced by the sensor and the solvent. Dosing rate (max) = 2 mL/min. which leads to a stronger reduction of the dosing speed..2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. the titration starts with a slower acceleration (ramp up) than in the normal mode. the slower is the titrant addition. Thus. The closer the potential to the end point. 3. In this case you can activate the Start: Cautious parameter. the end point must be adjusted. e.3 The Cautious start If the water content is very low. 19 . 2. 3. 3.

Auxiliary reagents • If formamide is added to the solvent. 20 . the overall ionic conductivity is decreased. which will lead to long titration times and to low precision. table) work fine. the system reacts slowly in the case of ethanol based reagents. the titration curve is more or less flat towards the end. If one-component reagents are used. used as solvent.g. • If 1-comp titrants are used. the sensor current shall be reduced to 15 μA. This measure allows the system to cope with the reduced conductivity. instead of methanol or ethanol. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. In order to achieve a good repeatability. Ethanol-based reagents • Compared to the methanol-based reagents. this results in an illdefined titration end point. If 2-comp ethanolic reagents are used. up to 8 mL/min for most 2-Comp 2 titrants. Therefore it is recommended to decrease the polarization current to about 15 μA. 2-propanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols. setting up of the titrant as 1-comp KF titrant yields shorter titration times. the titration can be accelarated by reduction of the control band to 300 mV. • • If 1-Comp titrants are used with Ethanol (e. • If Chloroform or Xylene is added in order to dissolve oil samples.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents. 3.g. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. the overall ionic conductivity is increased. Composolver E) the standard 1-Comp parameters (cf. This results in a lower voltage required to maintain the polarization current.4. • If 2-comp titrants are used. e. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents.

the 1-Comp control is suitable for systems that show an oscillating potential behaviour. which is the case in some ethanolic reagents. 3. 200.4.5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal. where the methanol has been replaced by e.6 General recommendations 1. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. Cautious Generator current: Automatic. 3. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. However the control band shall not exceed the start potential. 300. E E t Oscillating system behaviour. There is no need to accurately adjust the control band to the actual start potential. which is the case in 1-Comp systems. 100 mA) 21 . In general. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. If the titration takes too long. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. 2-methoxyethanol. 2. In most cases 300 – 400 mV are well-suited. Fix (400. The minimum dosing rate shall be used to fine tune the final phase of the titration. an increase of the control band is recommended.

The iodine generation starts slowly. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA. Later on.e. i. a delayed switch-off time of 10 to 20 seconds was set at the end point. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new.25 µL for a 5 mL burette).Fix). as soon as the was potential value was lower than the set end point during the defined delay time. relative drift stop. 3. i. pulse frequency and pulse height (mA) are used as variables by the instruments. the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter. the iodine generation is higher than in the cautious mode. Five termination parameters can be defined in the titration method: delay time. 200 and 100 mA. iodine is generated by means of current pulses of 400. pyridine-free reagents with a faster reaction rate. and improved KF titration stands (i. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.e. In addition. the slope of the iodine generation rate is flat at the beginning of the titration.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters.g. Initially. absolute drift stop. The closer the measured potential value from the predefined end point is. tightly sealed stand).e. minimum titration time 22 . Variation of pulse length (time).e. This parameter shortens the titration time and leads to repeatable results. high resolution burettes (0. maximum titration time. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. 300. i. In particular. More specifically.METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. Cautious: Suitable for samples of low water content (e. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. Normal: This iodine generation mode is generally used for all water content determinations. or it can be set to a specific value (“Generator current” . the slower is the generation of iodine. 2.. then the titration was stopped. less than 50-100 μg water per sample). Since the first developed KF reagents reacted slowly.

otherwise the termination criterion will never be reached.METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e. Typical absolute drift stop value: 3 µg/min (coulometric). After the defined time has elapsed. Typical value for the relative drift stop = 2-5 μg/min (coulometric). Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value.e. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. the titration is terminated and the result is printed. 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. 15 s) following the addition or generation of iodine. . 23 .m the drift before titration) and the relative drift. titrant concentration (volumetric) and side reactions. the absolute drift stop value must be greater than the initial drift. Typical delay time: 5 . especially if working with the KF sample oven. otherwise the termination criterion is never satisfied.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. • Advantage: This parameter ensures a high repeatability of the results.g. Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. 5-15 μg/min (volumetric) • Advantage: independent on the initial drift. Thus. The smallest increment must be sufficiently large to compensate the drift.Maximum titration time The titration is terminated after the defined time. Disadvantage: The value optimized to the initial drift. easy to understand (volumetric).

so 24 . but involves a risk that the titration will be terminated a bit too early. A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. soluble samples You should normally choose the relative drift stop as a termination parameter. • Advantage: This parameter ensures a high repeatability of the results. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular. Use the drift/time curve to determine this value. the drift at the end is often greater than the initial drift. It is recommended to be used for substances that release water slowly. Maximum titration time for determinations with the KF drying oven When using the drying oven. The vaporization of water is also irregular in the final stages. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. 3. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min).Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). The final traces are only extracted very slowly. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration. A relative drift stop of 20 to 30 µg/min shortens the titration time. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. possibly resulting in poorer repeatability and lower water contents. and the titrant concentration (volumetric). Thus. i. you can ignore these traces. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability.e. If the water content is relatively high. This parameter is independent of the the initial drift (coulometric. this is the simplest and most universal parameter to use.6. volumetric)..METTLER TOLEDO Good Titration PracticeTM in KF Titration .

Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. If the drift is greater than 10 µg/min. This is the case with samples that only release the final traces of water very slowly or that produce side reactions. It gives you the best accuracy and repeatability of results. the maximum titration time has proven to be best termination criterion in practice. (Set the minimum titration time equal maximum titration time). you should take measures to reduce the drift. 25 . The higher drift is therefore influenced to a large extent by the sample. If the drift stop value is not reached. the titration is terminated at the latest after the defined maximum time. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. Therefore.

the higher the atmospheric humidity in the laboratory. Briefly. Moisture can enter the sample.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. This can take 1 .4 weeks (indicated by a colour change of the indicator of the silica gel). it is titrated to dryness during pretitration. the residual moisture dissolves more rapidly into the anolyte (solvent). Do not shake too vigorously to avoid solvent gets on the cover of the vessel.e. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. The air-conditioning system should therefore be equipped with a moisture condenser. Condition the titration cell before use. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . the titrant and the titration stand. the greater is its influence on the results of the Karl Fischer titration. The drift. The following rules should be observed: • • Close all openings in the titration stand. whereas molecular sieves require temperatures up to 300 °C. Silica gel can be regenerated over night at 150 °C. The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air. The air within the titration vessel also contains moisture. However. When you assemble the titration stand for the first time. 26 .1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent). until it is absolutely free of water. since cold air cannot absorb as much moisture. however. In this way.1. the relative humidity increases. where the relative humidity can achieve values of more than 80%. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. there will be moisture on the glass surface of the titration cell and the inserts.3 hours. i. The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. After the anolyte (coulometer) or the solvent (volumeter) has been added. This problem is particularly relevant in tropical climates or in coastal regions.

traces of water will always find a way into the titration cell. the KF titrator continuously titrates the water that diffuses into the cell. On the other hand. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. At the start of a sample titration.(drift * titration time). For accurate results. the drift indicates the quantity of water that enters the titration stand over a defined period. This is achieved by titration of the dry solvent for a defined time (drift determination). this water amount is also titrated during analysis. it is necessary to quantify the amount of water entering the titration cell during titration. it is also possible to use the value of a previously performed drift determination (“Determination”). the last measured drift value is automatically stored. the drift value should therefore be as low as possible and stable before the start of a titration! 27 .1. Therefore it must be taken into account when calculating the water content.2 The drift No titration stand is completely water tight. In this respect. On the other hand. Therefore. t.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. and its value is displayed on the screen. In the standby titration. or a fixed value can be defined into the titration method (“Fix value”). or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . and is given in μg water/minute.

If the level of the catholyte is the same or higher.First transfer 5 mL catholyte to the cathode compartment.Make sure that the level of the anolyte is approx.2 Working with the coulometric KF instruments 4.When a sample is injected into the anode compartment. the level of the anolyte increases. Note: In production. 2. the level of the anolyte drops due to evaporation. the moisture enters the diaphragm and is slowly released into the anode compartment.Pour approx. . the anolyte should be topped up from time to time with anhydrous methanol. which leads to a higher drift. 100 mL electrolyte solution (anolyte) into the titration cell. As soon as the stirrer is switched off. • Titration cell with diaphragmless generator electrode .5 mm higher than that of the catholyte.1 Filling the coulometric cell • Cell with generator electrode with diaphragm . when the drying oven is used. This can be avoided as it follows: 1.Take approx. . By ensuring that the level of the anolyte is higher than the one of the catholyte. a flow occurs from the cathode compartment to the anode compartment. 28 . However. The catholyte always contains traces of water. 100 mL anolyte. the levels slowly become the same.5 cm into the electrolyte solution.The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation.2.Then fill the anode compartment with approx. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. If this is not the case. . you must add some methanol or sample so that the color changes to yellow. . 2. . 3 .The generator electrode should dip approx. Higher anolyte level → low drift Lower anolyte level → drift is high . Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. In this case. some anolyte solutions contain an excess of iodide and the solution has a brown colour.

If an emulsion forms in the anode compartment.Catholyte solutions (5 mL): after 200 mg water. This can happen if large amounts of samples of low conductivity are titrated. In practice. It is fully controlled by the titrator. the drift slowly increases.Anolyte solutions (100 mL): after 1000 mg water. e. The higher the level in the anode compartment. Any contact with the reagent is avoided during draining and refilling of the titration cell. and the risk of over titration increases. This can lead to wrong results.2. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . With poorly soluble samples. when using a generator electrode with diaphragm. the level of the solvent or the anolyte exceeds the 150 mL mark. the worse the stirring efficiency will be. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. If the conductivity of the anolyte drops to a very low value. A level sensor in the waste bottle prevents from overflow. below 10 μS. If the drift is too high.g.2. After being used for two weeks. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. . The capacity is monitored by the coulometers (see operating instructions).3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. . In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift. • • • • • 4. If an electrolyte is used for a long period without replacement.

30 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 2: The Anolyte is drained into the waste bottle by applying vacuum. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen.

The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. In this configuration only draining of the titration cell is possible. An optional reagent exchange set consisting of tubes.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . drying tube and tube holder enables both draining and refilling.

• Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. since it would cause a higher drift value. Methanol flows through the diaphragm and rinses out moisture and contaminants. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4.Place the empty generator electrode in anhydrous methanol. Drying is not necessary if you use it immediately. If immediate use is required rinsing with anhydrous methanol shall be applied. Afterwards thoroughly rinse the generator electrode with water. Simple cleaning and drying of the generator electrode Method A: . . the most effective cleaning agent is chromic acid. The C30 provides a reagent monitoring routine which is called Reagent Control. . The procedure is identical to that described above. Method B: . It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction.Methanol flows through the diaphragm into the cathode compartment.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated. • 32 . The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. .Fill the generator electrode with anhydrous methanol. Moisture and contaminants are rinsed out of the diaphragm.This procedure should be repeated at least once. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. which leads to a higher drift.2.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. especially if dirty samples are analyzed. then with anhydrous methanol and dry it as described above.

A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped. This also becomes noticeable through a dark coloration of the anolyte at the end point.5 mol/L sulfuric acid. This test of the complete system by a titer determination is therefore an essential condition for accurate. while the two-component titrant is rather stable).1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. a layer is formed on the platinum surface after the first few titrations.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. the tightness of the titrant bottle and the desired level of accuracy. • With heavily contaminated electrodes. . which prevents a good indication. so that there is a sharp drop in concentration. place the electrode in 0.g.5 Cleaning the measuring electrode Generally. it is better to determine the concentration every 2 to 4 hours. Their volume increases considerably with temperature. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. the measuring electrode must be cleaned. However. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. samples may be deposited on the surface of the electrode.01 mg/mL per week. 3. In this case.3. As already described. e. 2) Connect the S7 connection of the generator cell with the indication electrode. In the global settings within the setup menu of 33 . The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . We recommend to determine the titrant concentration daily. the one-component titrant. 2. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. repeatable results. Based on the chemical stability of the titrant. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. the indicating electrode does not need cleaning. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode.if the titrant bottle is not tightly sealed. The titrant is not chemically stable. 4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. This is sufficient in most cases. • Clean the platinum pin with a paper tissue.2.if the desiccant on the titrant bottle is "used up". This leads to a higher potential jump. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. The layer should therefore not be removed by cleaning. 4. The Ohmic resistance of the electrode is increased.

. Mix for 3 minutes to achieve complete dissolution before you start the titration.3. Determine the concentration under the same conditions as for sample analysis. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time. The plastic tubing is not absolutely water vapor-tight. This sample size yields an optimum titrant consumption of 1. Either the user is simply warned or the usage of the expired titrant is blocked. which prevents the execution of further titrations. Make sure that nothing adheres to the beaker wall or to the electrode. Determine the weight by back weighing and enter it as sample size.66% of water.3 to 2.04 and 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded. Note: 1. i.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.e. Na2C4H4O6•2H2O (M = 230. i.5 mL with a 5 mL burette. Rinse the burette 2 times into a waste bottle before you determine the concentration. - 34 . Since it slowly dissolves in methanol.08 g di-sodium tartrate dihydrate with the aid of a weighing boat.and at the same temperature. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. it contains 15.using the same titration stand with the same volume of solvent. 26-50 % of burette volume. 4. Under normal conditions. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure .08 g/mol). Add it into the titration vessel. 2.e.: .Use the optimized METTLER TOLEDO method M301 Weigh between 0.

You must either change the solvent after every sample or use pure Solvent* for the determination. They are thus protected against the ingress of moisture and can be stored for up to five years.0. Partially soluble. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. Highly soluble. The values that are obtained are approx. mixing time 1 minute. mixing time 5 minutes. Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL. 35 .0" from Sigma-Aldrich® with 10 mg water in 10 g standard. A cloudy solution will falsify the results (i. Thus. "HYDRANAL®-Water Standard 10. You cannot perform more than three determinations in 40 mL of methanol (with 0.3 Concentration determination with Water Standard 10. You can perform six determinations in 30 mL of Solvent* before you need to change it.5 g of water standard 10. You must perform the determination in pure methanol! Less soluble. mixing time 1 minute. Less soluble. The values obtained are approximately 10% too high. e. too high titer). mixing time 1 minute. The water standards are supplied in glass ampoules. Slightly soluble. Partially soluble.e.g.05 g di-sodium tartrate). mixing time 2 to 3 minutes.0 to 1. mixing time 2 to 3 minutes. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. you should weigh in 1. 30% too high. This content is confirmed by the test certificate enclosed with every package. You must perform the determination in pure methanol! Highly soluble.3. You can only perform one determination in 50 mL of 1:1 mixture (with 0. You cannot perform more than one determinations in 40 mL of ethanol (with 0.045 g di-sodium tartrate).0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water.05 g di-sodium tartrate dihydrate).

with a Hamilton microliter syringe). Draw the whole content of the ampoule into the 10 mL syringe. You can use a water standard with 1.5 mL at a time as an aliquot. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e. accurate results.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. In an open ampoule the liquid standard is exposed to air moisture. Glass syringes are better. To reduce the influence of the atmospheric moisture.4 Concentration determination with pure water General When using pure water to determine the concentration.01 mg (e. Inject 1 to 1. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL. 4. Thus.0 mg water/g for a titrant concentration of 2 or 1 mg/mL. Plastic syringes may introduce a small amount of moisture.0 mg/g water standard.3. Start the titration without any mixing time. Rinse a 10 mL syringe with approximately 1 mL of water standard. The sample should be weighed either using a balance with a resolution of 0. 4. A balance with a resolution of 0.g.01 g as the sample size. The content of an ampoule is sufficient for 3 to 5 determinations. the whole content of the ampoule is completely drawn into the syringe. – – – 36 . it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. or with a 10. 2.0 µL deionized water with a 10 µL syringe.g.1 mg does not satisfy the requirements for a repeatable titration. Start the titration without any mixing time. Inject exactly 10. a very good deal of practice and precise working is required to obtain repeatable. 3. 5. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. 6. Enter 0. Determine the weight by back weighing. the water content is increased and thus this will falsify the results. The error is minimized by rinsing and conditioning the syringe beforehand. Use a new ampoule for each new concentration determination.

wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. suppositories Sugar products: jelly. - 4. lay it down on the adapter and empty it completely. beverages Cosmetics: soaps. hydraulic oil. 2. the sample must release water completely. You can get rid of any bubbles in the syringe by expelling the water rapidly. Hold the syringe at right angles directly in front of your eyes to read off the value. corn.0 µL. salicylic acid Foods: honey. All the screws in the syringe must be tightened securely. ester Organic products: urea. Only freely available water undergoes reaction with the Karl Fischer reagent. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 .3. ethereal oils Petrochemical products: gasoline.5 The solvent To determine the water content in a sample. You can use mixture of solvents to achieve complete dissolution. Solvent Methanol Max. tar products. fatty creams Waxes. fat Oils: edible oil. Adjust the plunger to exactly 10. noodles. Do not warm the syringe. transformer oil. jelly bears Starch products: flour. to avoid touching the glass part. if it is absorbent. massage oil. diesel oil. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. yogurt.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. emulsions Petrochemical products: crude oil. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. Always use a syringe with a long metal shaft. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. amount 100% Samples Solvents: toluene. kerosene Pharmaceutical products: ointments. Insert the syringe through the 1 mm hole of the three-hole adapter. Always add each sample in exactly the same way. alcohols. creams. dioxane. caramel. After setting the volume. it may draw water out of the needle!). However.

50°C). you must replace the solvent timely. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong.e. The extraction capacity can be improved by increasing the temperature (e. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: . The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life.3. The amount of formamide at 50 °C should not exceed 30%.salicylic or benzoic acid for basic samples. The solvent for the two-component reagent contains SO2.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. i.g. The solvents that are used should contain as few water as possible (< 100 ppm). The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. Sugar is the only type of sample that dissolves in formamide. starch products will not dissolve in it. or the titration will take too long and titrant will be wasted. On the other hand. In this case.imidazole is used for acidic samples. 3. or by indicating the maximum number of samples to be titrated. the titration of subsequent samples will then be very slow. the water will no longer be completely released. and . 4. Once again. too low water content. 2. If exhausted. which may be completely expended if you titrate a large number of samples with high water content. the amount of water in mg which has been titrated. This will lead to incorrect results. Therefore.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. it is necessary to replace the solvent timely. If acidic or basic samples are titrated. formamide effectively extracts water from starch products. 38 .

2. The sample must be representative. The sample should be taken quickly to exclude. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample. In the case of non-polar solids. the lower the amount of moisture.e. the sample should be larger the more heterogeneous the distribution of the water. you will no longer be able to determine its true water content. which cannot be mixed as thoroughly as liquids.the most common source of error. "An analysis cannot be better than the actual sample!" When sampling. This can happen when a sample cools and the water solubility is decreased.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. such as butter. 5. rinse the bottles two or three times with the sample beforehand. water may be separated from the sample if it is left to stand for a long time. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. Heterogeneous water distribution in samples: In non-polar liquids. you should take into account the following points: 1. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed.1 Taking the sample When taking samples for water determination. Use bottles with a septum stopper for liquids of very low water content. Use sample bottles with small openings to minimize the ingress of moisture. In such cases. It floats on the surface or sinks to the bottom. With liquid samples. 5.2 Storing the sample After you have taken the sample.g. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. i. the water is not uniformly dispersed. the absorption or release of moisture. oils. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. 4. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. you should determine its water content as soon as possible. If you have to store the sample. With liquid samples that do not dissolve water such as oils. e. or at least minimize. you must be extremely careful to exclude atmospheric moisture . Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. and thus air moisture can penetrate the plastic and absorbed by the sample. keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight. it must contain the same average amount of water as the material as a whole. 3. 39 .

If a high level of accuracy is required. sample size Amount of water [ppm] [g] [mg] 1 10 0. approx. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.0 1000 1 1.5 to 2 mg water per sample. This corresponds to 0. Repeatable results can be obtained even with 0. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. the optimum amount of water is approximately 10 mg per sample.4 500 2 1. because the absorption of atmospheric moisture during sampling or sample addition becomes less important.01 10 8 0. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.1 to 0. the optimum amount of water is in the range from 0. In general. and the following minimum sample sizes should be used: Water content Min.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL.1 to 0. For optimum accuracy with determinations in the range from 1 ppm to 1% water.3 Amount of sample The amount of sample used depends on • • the expected water content.08 50 5 0. the accuracy is improved if larger sample amounts are used. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 . For coulometric analyses. A titrant consumption of 0.1 mg water per sample.0 10000 = 1% 0. 10-50 μg water can be detected if the demand for repeatability is not too high.0 For volumetric titrations.2 1. As a rule of thumb. it is recommended to use the minimum sample size given in the following table: Water content Min. This corresponds to 7.25 100 4 0.05 mg water per sample with a titrant concentration of 1 mg/mL.0 5000 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5. and the required accuracy and precision. Under optimum measurement conditions. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values.5 to 17. the accuracy increases with the amount of sample.1 1.05 mL is thus still acceptable when using a 5 mL burette. because the absorption of air moisture during sampling and sample addition becomes less important.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. Logarithmic scale! 41 . 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.

an optimum sample weight range is recommended. 42 . which is accessible in the online titrations screen: Dependent on the expected water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine.

aqueous emulsions. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. In the case of a volumetric Karl Fischer titrator. 43 . This prevents the sample from solidifying in the syringe during the weighing. especially with samples of low water content. benzene glycerol. silicone oil. ski wax. honey a Waxy candle wax. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. 50 °C and fill it into a syringe. you must take suitable precautions to prevent atmospheric moisture from being absorbed. In the case of a volumetric Karl Fischer titrator. creams.1 Liquid samples When adding liquid samples. toluene. Low water content Low water content Hygroscopic Viscous Very viscous ointments. Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. paraffin. Possibly warm the sample slightly to lower the viscosity. hydraulic oils. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. alcoholic beverages methanol. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. Inject it into the cell using a wide-bore needle. suppositories b c Liquefy the sample in an oven at approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. yoghurt. Fill the 5 or 10 mL syringe with sample after removal of the piston. The syringe is heated together with the wax. edible oils hexane.

Withdraw the plunger and rinse the syringe with the sample by shaking it. Fill the syringe with sample and wipe the needle with a paper tissue. Start the titration. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. the drop will adhere to the septum. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Fill a syringe without a plunger with molecular sieves. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. If the sample is hygroscopic or has a low water content (< 1000 ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. seal it with cotton wool and insert it into the septum bottle using a short needle. Enter the sample size in the titrator or transfer it automatically. you must aerate the bottle with dry air (equalize the pressure). Air flows through the molecular sieve into the bottle when you take a sample aliquot. Otherwise when the syringe is removed. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0". – – – – – – – – – – 44 . To avoid this. use bottles with a septum stopper and pressure equalization. Replace the syringe with the remaining sample on the balance and back weigh it. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. Empty the syringe (into the waste bottle) and repeat the rinsing two or three times.

g. this would lead to an error of 5% to 10%. crystalline samples: Weighing boat – Grind hard.g. in a volumetric KF titrator solids can be directly transferred into the titration vessel. depending on the ambient humidity. For instance. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. cellulose powder: – Either weigh the sample in a dry box or extract it externally. pulverize less hard samples in a mortar. e. jellied fruits. about 50-100 μg water enter the anode compartment.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6. Hard. thus. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. With an optimum sample size of 1 mg water/sample. it should be added under the same conditions as it was transported and stored. If possible. cooled analytical mill. the storage of samples in a refrigerator may cause water to condense.when the titration cell is opened to add the sample. salicylic acid. chocolate. solid fat: – Grate the product and add the sample with a spatula.g. Sample characteristic Brittle Hard/soft Pourable Procedure e. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode.g. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. salts. e. The sample should be quickly weighed and added to minimize air exposure. coarse-grained samples in a closed. 45 . For this reason.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . jelly bears. – Add the sample with a weighing boat. fatty e.

sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. butter. Do not use a syringe. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e. honey. Use a weighing boat with attached flexible tubing if necessary. ski wax. Start the titration.g. edible fat: – Homogenize the sample well: the water is heterogeneously distributed.g. margarine. suppositories: – Liquefy the samples in a drying oven at approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. Back-weigh the empty weighing boat. Enter the weight in the titrator or transfer it automatically. inhomogeneous e. 50 °C and fill them into a syringe. paraffin. - 46 . because the water is released if it is pressurized Waxy e. Add the sample into the titration vessel.g. to prevent the sample from adhering to the vessel wall or to the electrode. chocolate cream. – Add the sample with a spatula. Tare the balance to zero. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. The syringe is heated up together with the wax. candles. The water content is often lower atthe surface than inside the sample. fatty.

coffee beans: Crush in a mixer. Sample preparation Water: Example: Biological samples First of all. e. cooled analytical mill. fatty Mince the product. Fibrous natural products Suspensions 47 . organic salts. solid fat: Grate the product. e.g. berries: Reduce with a homogenizer in an external solvent.g. chocolate. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. in plants) Water Example: Sugar. e.g. e. water adsorbed on surface capillary bounded water (e.g.g. it is necessary to crush insoluble solids in order to gain access to the trapped water. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples. e.: • • • • entrapped water water of crystallization (salts). fruit juice extracts.g. minerals. hard salts: Grind in a closed. sausage. e. meat. e.g. brittle Moderately hard. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus. grain. vegetable juices: Reduce with a homogenizer.g.g. dried fruit and vegetables. e.g. jellied fruits. The following methods are available: Sample characteristic Very hard Procedure e. noodles. inorganic salts. cheese: Hard. brittle Viscous Hard. then reduce it further with a homogenizer in an external solvent. fatty Soft.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. This is not the case with solids if the water is bound as. crystalline products: Pulverize in a mortar.

1 4.3 2.0 1. etc. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.8 1. You can speed up the extraction of water from the sample by • • In many cases.2 1. using either methanol or a mixture of it as the solvent.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel. grinding the sample additionally with a built-in homogenizer (see photos below).0 7. sugar.8 4.3 1. Water is then extracted providing the mixing time defined in the titration method is sufficiently long. potato chips.4 1.5 8. heating the solution with a thermostating titration beaker.4 0. e. hazelnuts.9 srel / % 0. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.9 0.1 mg/pc 3.g.4 1.9 0.1 1.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .5 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.8 1.

Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. Pay attention to the water capacity of chloroform (max. Briefly.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. water is extracted from the sample by means of a defined quantity of solvent of known water content. the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. curry) for dehydrated products for sugar (total water). butter milk. 350 ppm) and toluene (max. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. 600 ppm). methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. 49 . pepper. In particular. edible fat) for natural substances (almonds.

A dilution factor of 10 . The larger the sample. - 50 . For the extraction of tablets. the smaller the relative error because the total error is calculated with respect to the sample size. Step 3: Extraction - Shake. or use a homogenizer. A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight).METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently.20 is normally used. Shaking is the method generally used for extraction. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. or use an ultrasonic bath with heating. Add a sufficient amount of sample.

take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . 51 . R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. % or ppm). Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix.

6 72.4 0.4 0.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.5 9. The weight of the solvent (msol).8 54.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.3 0.6 0.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.9 11.4 0. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .6 61.4 4.3 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.5 0.

by selecting the appropriate calculation (i. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function. “External extraction”) in the method function “Calculation”. Note: 1. The water content of the solvent should be as low as possible. 2. Chloroform. reaches the saturation limit for water already at 350 ppm! 53 . the formula is automatically given. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible.e. for instance. The amount of sample should also take account of the absorption capacity of the solvent. In particular. 3.

%: C = (VEQ*CONC-TIME*DRIFT/1000)*0. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results.9 5. or with a very low water content.2 10. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent). waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution.8 2. the addition of methanol is not necessary. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 .2 1. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. in % or ppm.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. or with a high water content Pure solvents can be used to dissolve the samples.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar.

7. Thus. the blank value correction is too large compared to the amount of water in the sample. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. because a large sample amount leads to a too long titration time. Draw an aliquot into the same syringe again.20 mL of anolyte titrated to dryness into the syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. Rinse the syringe two or three times in this way. 7. Draw 10 . 2. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Determine the weight by back weighing. Since you are able to work with larger amounts of sample when working with this technique. On the other hand. In fact. 6. Remove approx. the error obtained by direct titration if the titration stand is opened to add the sample is too large. Direct titration is not suitable. If the solid has a low water content (<200 ppm).4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. 5. the error as a result of opening the titration stand will be between 10 and 30 µg. and too much titrant is consumed. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. serum. 55 . foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. this error is reduced. Determine the weight of anolyte injected by back weighing. weigh it and inject it into the septum bottle. 4. 3. biological tissue. weigh it and inject it into the titration cell.g. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell.

zero must be entered for the blank value (B). Thus. 4. the water amount in the septum bottle is 4 times larger. 7. 8. 5. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. If you know the lyophilized sample amount in the septum bottle. Alternative procedure: 1. the final result must be multiplied by 4 (factor f = 4). In this way. 2. With a standard method calculation and calculate the water amount in µg. Remove approx. Since ¼ of the total amount was injected. Rinse the syringe two or three times in this way. then you can additionally calculate the result can be given in ppm. because the anolyte titrated to dryness has a blank value of "0".METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. 6. 3. The accuracy of a plastic syringe is enough. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. 56 . The water amount in µg is determined.

. .Purge the sample vessel and the tubings thoroughly beforehand with the gas.CO2 gas can not be titrated directly since iodine reacts with CO2. .Stop the gas flow after 1 to 2 mL titrant has been consumed. water-free absorption liquid in which CO2 itself does not dissolve. the gas must be directed through the titration vessel for a defined period of time. 57 . . to ensure that the titration is terminated after the maximum time.5 Determination of water in gases To determine the water content of gases. If not. you must fill the gas either into special gas sample tubes or into small steel cylinders. . 600 s as termination parameters. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time.With sample vessels the gas amount gas can be determined by differential weighing. . .METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. .g. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.Select "Max. hydrochloric acid.Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e.If possible.As soon as the drift is stable again.When titrating large quantities of gas in the same solvent. you should titrate the gas sample directly from the source. time" and a "Delay time" of e. to prevent the gas from flowing into the titration vessel. .g. Determination .Turn the three-way valve. evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. The gas must be directed through a water-dissolving.Calculate the volume from the time and the gas flow rate. Sampling/sample addition . . The water content in ppm is calculated by entering the volume and the density. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel.Purge the system with the gas before you start the determination. Notes . depending on the water content of the gas.Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min.

or 2.7 500 97.6 Determination using the drying oven This method is suitable for solids and liquids that 1. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results. 58 . and the amount of water is determined. that release water very slowly.6. If you use air for organic samples. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven.1 Principle The sample is heated in an oven.6. cf.2 Purge gas Air contains oxygen.4) A gas stream of approx.5 . cause side reactions with the Karl Fischer reagent.6. For Karl Fischer titration.6. chapter 7. chapter 7.1 bar (cf. inorganic samples. 7. the purge gases must be first dried before entering the KF oven. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99. e.9 166 99. you should use a two-stage pressure regulator so that the final pressure is in the range 0. causing the water in the sample to vaporize. which could react with the sample at higher temperatures. Thus. the oven temperature should not exceed 160 °C. The water is transferred to the titration cell in a current of dry inert gas (purge gas). If you use nitrogen from a gas cylinder. Air should therefore only be used for non-oxidizable. 7.g.0 mg/L Therefore.4 – 8. for accurate results do not select a too high gas flow rate. 11 mg/L nitrogen gas from a cylinder: 1.1 - The recovery rate is clearly decreasing with increasing gas flow rate.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. The purge gases commonly used contain moisture.: o o air with 50% humidity: approx.5).

there are two types of anolyte solutions: 59 . With some samples the drift at the end of the titration is significantly higher than the initial drift. they are rapidly exhausted. the titration starts and the released water is continuously titrated. especially methanol. In the case of KF coulometers.e. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . all the water is vaporized and transferred to the titration cell. deactivate the drift stop).60 s). in contrast to other desiccants. In order to avoid the latter you may also use the minimum time as termination parameter. Silica gel can be regenerated over night at 150 °C. the vaporization is often very irregular. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. 2. but their water absorption capacity is low.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. Silica gel is appreciably better in this respect. 100% Phosphorous pentoxide. To ensure that the determination is repeatable. you should set the maximum titration time as the termination parameter (i. This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample.6. deactivate the drift stop).50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. 7. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. Silica gel and molecular sieves have the advantage that they can be regenerated.80 µg H2O/L 40 . It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. i. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell.e. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. At the end of the titration.e. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum. whereas molecular sieves requires temperatures up to 300 °C. In such cases you should use the maximum titration time as termination parameter (i.METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. The KF titration is then started. Method 1: The water evolved is continuously titrated After a short mix time (20 . The relative drift stop or the maximum titration time can be used as the termination criterion.

5 190 280 140 300 300 200 15 10 15 20 10 15 Max. time Max. time Max. Examples: Sample Result / ppm No. time Max. Coulomat AG Oven): Anolyte loss at 150 . of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!). Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 .6. An air pump is available as an optional accessory.e. i.4. you should replace the anolyte lost through vaporization with new anhydrous methanol. 3.5 .200 mL/min.95 98.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. 7. as well as a gas flow meter. oven temperature 200 °C: approx. and the better the recovery. time Max. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. Due to the vaporization of the methanol.g. dedicated anolyte to be used with a KF Oven (e. 1 mL/hour – From time to time.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C.g.200 mL/min.2 99. oven temperature 200 °C: approx.7 99.5 mL/hour Anolyte containing ethylene glycol.e. fibers) or with samples of low water content. time 60 . the faster the water is titrated. i.2 4. the recovery is not 100%.g. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve.2 1.8 6. time Max.9 2. This is particularly important with low-weight samples (e. The recovery therefore depends on the amount of methanol vaporized and the method used. The procedure for the determination of water content is described in the operating instructions.9 9.1 Briefly: The less methanol is vaporized. It has a large glass sample boat capable of holding up to 10 cm3 of sample. there is a small loss of water.

5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. If several determinations are performed in the same solvent. the evaporated solvent lost in the gas stream has to be replaced. . In such cases. Then. If the water is titrated as soon as it begins to evaporate. Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. start the titration so that the drift value is automatically entered. To check the performance of the titrator/drying oven system. 10. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. in volumetric KF titration the methanol loss is approx. A large amount of evaporated water cannot be fully absorbed by the solvent. If the drift is higher than 15 μg H2O/min. Close the stop cock and purge the "hot zone". do not select the parameter "Auto start". 4. For instance. Set a gas flow rate of 150-200 mL/min. 3. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5. 6. evaporated solvent does not condense in the drying tube. 2.7%. and/or replace the anolyte of the KF coulometer. Open the stop cock. 3. For the same reason. This leads to a too low result. Some samples require some time before water starts evaporating. the recovery increases to 99. purge the "cold zone". Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). bent drying tube. replace the silica gel and molecular sieves of the gas drying unit. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. If the drift is constant.55% or VWR/VWR/MERCK water standard KF oven 1%. 61 9. Some samples have surface water that is lost as soon as the oven is purged with dry gas. you should proceed as follows: 7. 5. This can happen when the titration is started only after complete evaporation.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1. and does not drop into the cathode compartment/ titration cell. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8.

STROMBOLI is completely controlled by the titrator: all the parameters for the determination. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. including the oven temperature. 3. are included in the titration method. The sample vials are moved upward into the oven by a lift. 62 . 2. The oven heats the sample to the set temperature. The blue rubber cap seals the sample vial tightly against the oven. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value.6. while a glass tube pierces the aluminum foil cover. 1 During a sample series: 2 3 1. Besides 14 places for glass sample vials. After the analysis. The drying oven can be operated in the temperature range from 50 to 300°C.

To determine the drift value accurately. The drift value is defined as the moisture entered into the titration cell by the purge gas.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). This is particularly important with light samples (e. Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack. fibers) or with samples of low water content. the moisture in the empty sample vial has first to be removed. This takes 10-20 minutes as can be seen in the following diagram: 63 . The sample vials are sealed with self-sealing aluminum foil and a rubber cup.

the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. These method templates are based on a dedicated KF method type called ‘Stromboli’. If. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. for example. The optimum blank value is in the range of 70 . suboptimum conditions.g. The first sample of the next loop is then transferred into the oven and the water determination begins. At the start of the method. moisture in the sample vial.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i.e. as well as the anolyte in a coulometric analysis.) are always slightly different. Important: After a blank value determination. the drift value can change with time. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. and thus the moisture adsorbed on the glass walls is not always the same. different plastic samples have to be analyzed. the blank value determination also takes the actual drift into account.300 μg water. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. The blank value can also vary as a function of temperature. they can be measured at different temperatures using the same method. In this case.the analysis times for the determination of the blank value and for each sample are the same. you can enter the number of samples the series includes for each loop. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396). With rapidly changing.e. a blank determination can be performed between two sample loops. drift value x time). the method contains a so-called sample loop. Nevertheless. i. etc. one with the same properties as the sample vials into which the samples have been filled in). The new blank value is automatically used for the blank correction. If the temperatures of successive loops are different. If the maximum titration time is used as termination criterion in the method -which is what we recommend. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures. In this case. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. it is important to use a new sample vial for each blank value determination (i.e. the moisture in the air present in the vial. By performing a drift determination at the end of the series or between several series. > 15 μg H2O/min). gas flow. Performing the drift and blank value determination In general. the moisture content is somewhat lower. In the same way. the vial used no longer has the same properties as the "fresh" sample vials. you can check whether the drift is constant and the new drift value can be used for the next series. For each series. It is therefore not necessary to perform a drift determination before each series. several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. 64 .e. whose optimum bake-out temperatures differ. This means that the stored drift value of the previous determination will be used. If this is the case. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. The blank value should be determined before each series because the humidity can change. Thus. To determine the blank value as accurately as possible. The loops run through one after the other and the samples are processed sample for sample.

55% or VWR/VWR/MERCK water standard KF oven 1%. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. To check the titrator/drying oven system. 4. 3. In this way. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. Set a gas flow of 40–60 mL/min. The delivery tube has a T-piece that causes a small leak flow. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. see also list of results). drying and storage). toluene. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. A sudden shutdown of power immediately switches the valve in that way. since it provides a leak free inert gas stream during normal operation. 5. These are partially vaporized (e. This has a large effect on the blank value and thus on the result. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. and therefore it does not drop into the cathode compartment. 2.g. 7. With STROMBOLI. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. evaporated solvent is not condensing in the drying tube. motor oil) or completely vaporized (e. This valve shall be used especially if inert gas sources are used. 8.g. you can not only determine solids but also liquid samples. A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. Use the same vials for a sample series as well as for the blank value determination. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. 6. bent drying tube. This test also serves to check the tightness of the oven and the connection tubing 65 .

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

68

25 0. it is necessary to use the optimum sample size in order to achieve precise results.0 3. Therefore.0 5. 69 .0 Sample size (g) In both cases.5 1.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs. with decreasing sample size the relative standard deviation srel becomes worse.0 2. A good repeatability is achieved the sample size is increased particularly for low water content values. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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Use rel.g.Homogenize sample. e.Increase amount of sample to ensure that approx.Level of anolyte should be higher than that of the catholyte . if possible increase amount of sample Wrong sample preparation and sample addition . increase t(max) Wrong control parameters .Clean titration cell and generator electrode and dry at 50 – 80 °C .Check whether titration stand is completely tight. drift stop . .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Use smaller sample Long titration time. . titration never ends Very long pretitration Poor repeatability Wet anolyte .Add a small amount of one-component KF titrant to the catholyte. Water distribution in the sample is not homogeneous .Increase value for rel.Clean the platinum pins of the measurement electrode with paper tissue .Increase end point Oven: water vaporizes very slowly and irregularly .Grease the tapered joints Moisture from cathode compartment and diaphragm . 1 mg water per sample is present.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10.Use a different method Oven: water not completely vaporized .Increase vaporization time. especially at low water content (< 1000 ppm) 73 . .Use higher oven temperature .Replace anolyte Amount of sample too small .Higher oven temperature .Measurement electrode is faulty Titration stand not protected against moisture . drift stop as termination parameter.Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Measurement electrode is not plugged in .Lengthen vaporization time (increase t max) .Use t(max) as termination parameter .Check whether titration stand is completely tight.Replace anolyte .The repeatability is strongly dependent on suitable sample preparation and sample addition. Oven: .Replace molecular sieves and silica gel in drying tube .

do not splash to the walls of the cell.Use fix generator current 100 mA . Sample not dissolved (emulsion) .Replace anolyte .Replace or repaire generator electrode. For samples with very low water content < 30 ppm .Sample not thermal stable: Use lower oven temperature . the Coulometer must be adjusted With water Standard KF Oven 1 %.1 mg/g .Lengthen vaporization time (increase t max) . . 10 – 15 minutes . .METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . Checking drying oven Out of limits. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .0.Use back weighing.Too low value: see above “too low value” if this does not help. drift stop . contamination with atmospheric moisture occurs.Use higher oven temperature .Use start cautious Oven: . It has no influence to the result.Add sample into KF reagents.use a bigger sample size up to 0.Check drift and blank value .Replace or change the anolyte .Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: . at 170 °C.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits. bad repeatability With water standard 1.Replace anolyte If this doesn’t help.3 g Generator electrode is contaminated The black cover cannot be removed.Too high value: see above “too high value” .Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. if it is defective. Anolyte has too low conductifity .2 .Extend tmin (minimum titration time) Incomplete sample addition .Use smaller sample size Values too high The titration was too fast → overtitration . check generator electrode. If the sample preparation and addition is not done carefully.Reduce the value for rel.0 or 0.

Reduce sample size Poor repeatability of the results Amount of sample too small .2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . e.Use t(max) as termination parameter .Extend vaporization time (increase t max) .Use higher oven temperature . e. if possible increase amount of sample.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.Use "Rel.g.see above Oven: .Homogenize sample.Increase value for relative drift stop. drift stop" as a termination parameter. Side reaction of the sample with the KF reagent .Clean platinum pins of the electrode with a paper towel. external extraction.The repeatability is strongly dependent on suitable sample preparation and sample addition. titration never ends Wrong termination parameters .Increase oven temperature . . Low water content (<1000 ppm)! .g. drying oven.Increase endpoint potential Oven: water vaporizes very slowly and irregularly . etc.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker. Oven: water is not completely vaporized . Water distribution in the sample not homogeneous .Check whether titration stand is completely tight. Titration stand not protected against moisture .Check and optimize control parameters.Increase amount of sample to ensure 10 mg water per sample.Replace molecular sieves and silica gel in drying tube .Use different method. .Increase vaporization time.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture . . Wrong control parameters . 75 .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water . increase t(max) Long titration time.Extend tmax (maximum titration time) .Grease the tapered joints Condition Titration stand .

Change solvent or use fresh solvent after every sample.Sample is not thermally stable: Use lower oven temperature . . drift stop . 15 – 20 minutes .Replace the solvent frequently.55 % at 220 °C. Oven: .Replace solvent . For samples with low water content < 400 ppm . bad repeatability 76 . Sample not dissolved . No more sulfur dioxide in the solvent .Reduce sample size Single values too high Control parameters too fast (= slight overtitration) . contamination with atmospheric moisture occurs.Reduce the value for rel. If the sample preparation and addition is done carefully.Increase sample size up to 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .0 is a simpler and a more dependable method. Poor sample preparation and addition . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results.Check drift and blank value .Use higher oven temperature .Extend tmin (minimum titration time) Incomplete sample addition .Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Samples of low water content (<1000 ppm) are always hygroscopic.Reduce dVmax and dVmax factor. With water Standard KF Oven 5. Di-sodium tartrate has only limited solubility In methanol max. The concentration determination is correct only if the di-sodium tartrate has completely dissolved.Use back weighing. Determination of the concentration using di-sodium tartrate or Water Standard 10.Use titrant with 2 or 1 mg/mL Oven: .Extend vaporization time (increase t max) . which dissolves the sample.Change solvent.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits. 0.12 g in 40 mL.Add chloroform or other solvent to methanol.

nitrotoluene. C0 Peroxides V2.V5 C20. C0 Sulfur compounds Phenols V0. diphenylmethanol Weakly basic pKa >8: Imidazole. V4 C20 Mercaptans V0. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0. o-cresol Side reaction: naphthol.V4. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 .V3. V3. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. C24 Hydrocarbons > C12 Biphenyl.V4. bitumen V4. C0 V2 C20 V15 Low pKa value: phenol.C22 V16 C0 V10 C0 Nitrocompounds V3. C20 V11 C0 V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.V3. indole.V5 C20 Ethers Linear and cyclic V2.V8 C20 V10.V4. V4 V2.V4. V3. toluidine Oxidizable with iodine: aminophenol Method V2.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. C0 V2. R-Br. V4 C20 V2.g. salicylic acid High pKa value: 2-chlorophenol. e.: benzamide. nitrobenzaldehyde > C12 Stearyl alcohol.1 Solid samples 11. V3.pyren e. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0. oxalic acid Oxidizable with iodine: ascorbic acid V2.V5 C20.C22 V2. cresol. anisidine. V4 C20 V15 C20 V0. naphthalene > C20 Tar. V5 C20 V2.V3.V7 V2. anthracene.V3 C20 di-Nitrobenzene. R-I R-NCO Benzophenone Method V2.1.

bitumen lubricating grease. CaO NaCl. e.C40 V2 Adhesives All-purpose glue. herbicides Soluble: wool dyes. V32 C21. indicator dyes. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. polypropylene. etc. PVC. C34 V2. H3BO3 NaOH. dispersion dyes Waxes. V5 V12 V2 V40. disinfectants Salves. fungicides. Phosphate. V5 V5 V2 V20 V2 V5 V30. Silicon dioxide Silanols R3Si(OH) Na2SO4. KOH MgO. Na2HPO4 tert. Insoluble: pigments. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. CaCl2 . KJ. paraffins: shoepolish. V32 C21.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. ski wax Tar. creams Suppositories Tablets Lyophilized preparations V2 V4. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene.g. V31 C20.: Na3PO4 Silicon oxide.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. V31 C20. etc. C34 V2. NaAsO2 KHCO3 . V31 C31. NaHCO3 Na2CO3 B2O3 . V32 C20. V32 C20. poly-amides.1. C32 Pharmaceuticals Antibiotics. C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. multipurpose grease V2 V2. C34 V31 C33 V2. V31 C32 V2.1. polystyrene. V30 Insecticides. NH4NO3 Nitrites NaNO2 11. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . V31 C20. polyurethane. V8 Cosmetics Creams. C34 V10 Na2HAsO3 . lotion Lipstick Soaps Toothpaste V4. C32 V15. HBO3 . 78 . ZnSO4 V2.

5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. mixed spice Mustard Adherent moisture: plain salt. V23 Vegetable products V22. ice cream Dried albumen Powdered milk V2 V13 V2.1. Zwieback. perborates) without brightener Total water V30 V2 11. margerine. tobacco. (V30) Cheese. hardened fat V4. wheat.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . jelly Sugar: adherent moisture Chocolate Spices Pepper. tea. sea salt V23 V24. noodles. Zwieback Yogurt. sea salt Total water: plain salt. rye. caramel. V21 Mortar. corn. broth Biscuits. gummi bears. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. meat spread. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. V23 V30.4 Technical products . mayonnaise Shortening.almonds instant coffee Fats Butter.. candy. C30 V2 V20 Paper. pudding powder.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. silk 11. plaster. V23 Cacao. noodles. curry. jam Honey. (V25) V22. almond paste Instant ice tea.1. potato chips Potato flakes Dough. dried vegetables and fruits Hazelnuts. wood Cellulose powder Wool.1. instant coffee. coffee beans. jellied fruits.

t-butyl chloride. HNO3. acetophenone. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. cyclohexane. chlorotoluene Acetone. cyclohexene. xylene C7 to C14 gasoline.2 Liquid samples 11. HCl Nitrobenzene. toluene. hexanol. acetic acid > C2 propionic acid. toluidine. ethylal. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. chinoline Strongly basic: alihatic amines N-butylamine. paraffin Aldehyde Acetaldehyde. isobutane. anisole Methyl benzoate. methylethylketone Ketones V10 C10 80 . nitrotoluene. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. chlorobenzene. dodecane > C14 heavy oil.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. pentane. disulfides sulfonic acids Mercaptans V1. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. ethyl acetate Methyl chloride. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.2. crude oil. methylal C1 to C7 hexane. hexylamine Reaction with methanol: aniline. benzene. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. dioxane. diamine Easily oxidized with iodine: hydrazine. petroleum. C1 Sulfurcompounds V1 C1 V0.

cream. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides.3.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. 81 . shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk. sample input and titration methods. tinctures Cosmetics: perfume. transformer oil. brake fluid. refer to chapter 11. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. wine. liquor Pharmaceuticals: extrakts. massage oil Vegetable oils Technical oils Hydraulic oil.2. sunflower oil Pharmaceuticals and cosmetics: ethereal oils.

120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . In this case methanol is used as a solvent.120 s Delay time: 7 seconds. Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 . dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 .10 minutes Direct titration methanol free Titrant: two comp. reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 . These can be also performed using the one-component reagent.1 Volumetric methods The methods have been developed using 2-component reagents.120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.3 Titration Methods 11.3.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .

120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe. Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.20 min With drying oven at 160 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 .20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 . 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 .METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .

Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate.3.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .

shake or sonicate. meat grinder. wool. 1-decanol.) S8 S9 S10 syringe with needle Ø 0.4. chocolate Method S1 S1. S11 S6. resinous Waxes Examples Butter. S10 S11 S4. almonds. Let solids settle and remove aliquot of remaining solution with syringe. Pulverize with mortar. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. No further preparation necessary. coffee. margarine Phenols. Homogenize sample well. Dissolve sample or extract water. 60° C.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. tobacco. silk Cheese. S2 S1. S3 S10. almond paste. SiO2 Salts. or up to approx. meat Jellied fruits.1 Solids: Characteristics Property Very hard Hard.: CaCO3 . Melt sample. yogurt Salts. S8 S10 Property Soft. After sample removal keep sample sealed. Use syringe with needle Ø 1. After sample removal keep sample sealed. tea. S5 S10 S8 Paraffins.4. S11 S4. brittle Soft. formamide). In external extraction solvent (methanol. noodles. Zwieback Dried vegetables and fruits. S10 S11 S10. for very thick pastes drill hole in bottom of syringe. 1-decanol. ice cream. Use grate to reduce size. Inject into titration cell. greasy Soft. cooled analysis mill.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. formamide).5 mm or without needle. Pulverize with mixer. Press through small holes e.8 mm ) Fill in backend of syringe Procedure Grind in sealed. paper. (Pre-heat syringe with hair dryer or in drying oven. (Select stir time so that sample dissolves completely. active ingredients Na-tartrate S9 S12 11. jelly.g. honey.) Homogenize sample well. Cut in small pieces with scissors or knife. potato flakes Tar. greasy Examples Minerals. rocks e. broth Hardened fat.g. cristalline products Wheat.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 . pepper. shoepolish Creams. S10 S2. Stir. pastes Pulverized soluble Salves. bitumen Method S7. gummi bears. creams gel. S3 S2. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. napthalene. At room temp.4 Sample preparation and input 11.

Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes.4.8 mm).8 mm) Inhomogeneous emulsions .The pressure loss during sample removal must be compensated with dried air.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. H2SO4. Hygroscopic sample or low moisture content (< 1000 ppm) . .Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. milk. Boiling point 5 .3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. . . after-shave Beverages. detergents.Homogenize thoroughly by shaking or stirring prior to sample removal. 0°C in ice bath. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. acetic acid Silicon oil.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. toluene.Keep sample in a septum flask.4.5 Accessories for sample input Syringe Injection needle Weighing boat. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 . synthetic enamels.Cool sample to approx.Remove sample immediately. . . 11.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0.15 °C . crude oil.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. acetone. glass Visco-Spoon™ 1 mL ME-71492 1. glycerine Acetaldehyde Methanol.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.15°C Examples Propanol. gasoline. glycerine Hexane.8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 .5 mm) Injection with syringe after cooling sample (with needle Ø 0. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Injection with syringe (without or with needle Ø 1. aqueous emulsions Acrylic enamels. For each titration use 1 mL syringe (with needle Ø 0. acetone. .Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. salad oil Perfume. petroleum. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11.4.

396 (1935). Chem.. VERHOFF. Anal. G. 123-125 (1981). “Reaktionsmechanismen in der Karl-Fischer-Lösung“. Acta. Chem. “Mechanism and reaction rate of the Karl Fischer titration reaction. J. 306.6 References [1] [2] FISCHER. 94. VERHOFF..W. Part V. „Karl-Fischer Reagentien ohne Pyridin.. R. D. [8] SCHOLZ. J. 394 . 215 – 219 (1959).. “Mechanism and reaction rate of the Karl Fischer titration reaction. Anal. Chem. M. 305-315 (1976). Angew. Potentiometric measurements”. Z.396 (1981). G. J. BUNSEN. Chem. 61. 395-403 (1977). VERHOFF. SEUBERT A. Fresenius Z. “Mechanism and reaction rate of the Karl Fischer titration reaction. 312. BARENDRECHT. SCHOLZ. 394 . J.. G. Chem. BARENDRECHT.comparison with the aqueous system“.. 203 . Ind. Anal. SCHOLZ. 265 (1853). „Kinetics and stoichiometry in the Karl Fischer solution“..C. Chem. PhD. 705-717 (1976). BARENDRECHT. 303. „Mechanism and reaction rate of the Karl Fischer titration reaction. 2407 .. Part II. Electroanal. Verlag Chemie Weinheim (1954) / (in German). 334.C. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. Electroanal. “Mechanism and reaction rate of the Karl Fischer titration reaction.C.. E. „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“.. J.C. F. Einkomponenten Reagentien“. 1999 (in German). A. First and second order catalytic currents at a rotating disk electrode“. Anal. Fresenius J.. Fres. Soc. COFINO. W.M. [9] WÜNSCH. J. VERHOFF.. Both publications from: SEUBERT. See literature references in: EBERIUS. 93.. GRÜNKE. . Fresenius Z. VERHOFF. Chem. Part III. Part I. Chem. Anal. WÜNSCH. Amer. W. „Karl-Fischer Reagentien ohne Pyridin. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. 30-32 (1981). Chem. C. S..S. Anal. 48. Anal. Fresenius Z. Chem. 334.. Chem. P. BRYANT. Fresenius Z. Th. 1988 (in German). Chem 368. 272 – 274 (1943). Chim. 1. 75-80 (1978). 460-464 (1982). E.. Electroanal... Zweikomponenten Reagentien mit Imidazol“. 71. Auflage. E. W. 309. 86. Thesis University of Hannover.207 (1980).. 139-147 (2000). J. Electroanal. „Wasserbestimmung mit Karl-Fischer-Lösung“. Nature of the Reagent”. „Karl-Fischer Reagentien ohne Pyridin. Chem. Eng. BOYD.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. “Untersuchungen zur Karl-Fischer-Reaktion”. 86. 75. J. E. Anal.2412 (1939). J. 15 (4). Chem. E.. E. E. “Analytical Procedures Employing Karl Fischer Reagent I. Rotating ring disk electrode meassurement“. 16-21 (1989) (in German). K. G. Fres. M. WERNIMONT. Ed..4. “Karl-Fischer Reagentien ohne Pyridin“. E. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. Anal. J. [3] [4] [5] [6] [7] 87 . SCHOLZ. Fresenius Z.. Liebigs Ann. Neue Eichsubstanzen“. [10] GRÜNKE. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“. WÜNSCH.. Z. SEUBERT A. Anal.C. 309. S. Analytical implications”. Rotating ring disk electrode meassurement . MEYER. 31 (2).. 407-415 (1978).J. KOK.. Chem. MITCHELL jr. Diploma-Thesis at the University of Hannover / Germany. 256-260 (1989) (in German). HOPFKINSON. SMITH. Chem. SCHOLZ. Anal. „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. Part IV. Chem.. A.. E. J.

METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. „Untersuchungen einer Karl-Fischer-Reaktion“. G. E.A. „Wasserbestimmung durch Karl-Fischer-Titration . RÜEGG K. Springer Verlag Berlin. Sigma-Aldrich Laborchemikalien GmbH. 1989 (German) 88 .Theorie und Praxis“. SCHÖFFSKI.. Diploma-Thesis at the University of Hannover / Germany. GIT Verlag GmbH. M.. 431-435 (2006). DE AGOSTINI A. „Eugen Scholz Reagents for Karl FischerTitration“.. K.30918 Seelze / Germany.. „Karl Fischer Titration“. SCHOLZ. D.. 11.. 1984. Food Chemistry 96. DE CARO C. Darmstadt / Germany. 2006. 1985. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications".5 Additional literature HYDRANAL®-Manual. WIELAND..

Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. The sample P used for the extraction is not dissolved. % or ppm). For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. WP: This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. 89 .1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction.

01% VWR/VWR/MERCK APURA water standard 0.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. The sample P used for the external dissolution is completely dissolved into the solvent. in % or ppm.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0.2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample. 90 . Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. Total water content (sample + solvent). Thus.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. the total volume is increased. Blank value (water content in% or ppm) of the solvent.

30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . If the sample does not completely dissolve. alcohols.e.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. 12. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12. ointments. i. A number of different anolytes are available to dissolve the various types of samples encountered in practice. edible oils. the water content determined is lower than the actual water content of the sample. esters. more solvent can be added to the anolyte. ethers. hydrocarbons (C10 to C20).1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10).4. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. acetamide.4 Reagents and solvents for coulometric analysis To determine its total water content. This means that if an emulsion is formed in the anolyte. the anolyte must be immediately replaced. the sample must completely dissolve in the anolyte.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. In this case.4. Alternatively. part of the water content is not measured. etc. an emulsion is formed. etc. This is limited to a maximum of 30% to prevent the conductivity from falling too low. chlorinated hydrocarbons (up to C10). For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. nitrocompounds.

hydrocarbons (above C20).3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. silicone oils. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences.4. we recommend the use of a second titration cell. For cells without diaphragm: - Notes on ketones: - - 92 . This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. etc. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12. Chloroform must be added to the anolyte to ensure the solubility of these samples. If you measure ketones regularly.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.4. transformer oils.

Measure the pH with a glass electrode adjusted with aqueous buffers. - - Notes on aldehydes: - - 12. etc.g. e. After a longer standby period. To do this. the drift is higher because of the very slow side reaction. the substances can. acetic acid.e. easily be measured with volumetric KF determination. The use of imidazole increases the pH value in the anolyte. 1 mL).5 to 7 (see Section 1. however.4. the pH value of the anolyte must be adjusted to the range 5. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). Basic samples must be neutralized with salicylic acid or benzoic acid. The special reagent for ketones can also be used for other samples. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Fill the anode compartment with approx. The measurement should not be performed in the titration cell because the electrode introduces too much water. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Choose relatively small samples (approx. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. Fill the anode compartment with approx. 80 mL of anolyte and 20 mL HYDRANAL® buffer. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. Short chain aldehydes (e. amines: - 93 . with reactive ketones such as cyclohexanone use only 0. With Karl Fischer titrations of acidic and basic samples. Aromatic aldehydes (e.g.2 mL to 0.: - For basic samples. i. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. Use the HYDRANAL® buffer (SIGMA-ALDRICH). - For acidic samples.2).g.5 mL. formic acid. Coulometric KF titration cannot be used to determine these compounds.g. benzaldehyde) can also be determined by coulometric KF titration.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. acetaldehyde) are oxidized at the anode with the formation of water.METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. The larger the sample. take an aliquot of anolyte from the titration cell. e. the more important the effect of side reactions becomes. In these cases the pH value of the anolyte should be measured.

5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12. nitrocompounds. In this case. more solvent can be added to the anolyte 12. part of the water content is not measured. ethers. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples. edible oils. chlorinated hydrocarbons (to C10). alcohols.e. acetamide.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. i. The water content is declared on a test certificate supplied with every vial.2 For samples poorly soluble in methanol or ethanol These include: etherial oils.6. Alternatively. etc. the anolyte must be immediately replaced. ointments.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10).6. If it does not completely dissolve.0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. esters. etc. an emulsion is formed. In this case. hydrocarbons (C10 to C20). A number of different anolytes are available to dissolve the various types of samples encountered in practice.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. This is limited to a maximum of 50%. 12.55% (potassium citrate monohydrate). the result determined is lower than the actual water content. One-component reagents: 94 .

This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. One-component reagents: 95 .6.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water.6.3 For samples insoluble in methanol or ethanol These include: petroleum oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. silicone oils. Chloroform must be added to the anolyte to ensure the solubility of these samples. transformer oils. etc. hydrocarbons (above C20). or an acetal. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.

If you have titrated a number of ketone samples. Short chain aldehydes (e.e. Choose relatively small samples (approx. 80 mL of anolyte and 20 mL HYDRANAL® buffer. To do this. easily be measured with volumetric KF determination. the substances can. benzaldehyde) can also be determined by coulometric KF titration. Coulometric KF titration cannot be used to determine these compounds. In these cases the pH value of the anolyte should be measured. the more important the effect of side reactions becomes. Fill the anode compartment with approx. Measure the pH with a glass electrode adjusted with aqueous buffers. If you measure ketones regularly. With Karl Fischer titrations of acidic and basic samples. e. e. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. acetic acid. The use of imidazole leads to a high pH value in the anolyte.6. however.5 mL.2). It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.5 to 7 (see Section 1. amines: 96 . - Notes on aldehydes: - - 12. It is important to note that alcohols that react with ketones should not be titrated in this reagent. Aromatic aldehydes (e. The measurement should not be performed in the titration cell because the electrode introduces too much water. the drift is higher because of the very slow side reaction.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. with reactive ketones such as cyclohexanone use only 0.g.2 mL to 0.g. 1 mL). This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).g. - For acidic samples. Use the HYDRANAL® buffer (SIGMA-ALDRICH). etc. The special reagent for ketones can also be used for other samples. acetaldehyde) are oxidized at the anode with the formation of water. The larger the sample.: - For basic samples. the pH value of the anolyte must be adjusted to the range 5. we recommend the use of a second titration cell.g. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. i. formic acid. take an aliquot of anolyte from the titration cell.

13.: 11 °C MAK value: 200 ppm Highly flammable.2 Two-component reagent: Composition: iodine and solvent (methanol. Safety: flammable to extremely flammable. Irritant when inhaled. Disposal: as an organic solvent. Irritant when inhaled. Health hazard upon inhalation. Keep container tightly closed.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. 13 Hazards and waste disposal tips 13. Do not let reagent contact skin or eyes. Fill the anode compartment with approx. 90 mL of anolyte and 5 g salicylic acid or benzoic acid.: 28 °C MAK value: 100 ppm Flammable. Safety: Highly flammable. Keep container tightly closed. Do not let reagent contact skin or eyes. swallowed or allowed to contact skin.: 46 °C MAK value: 5 ppm Flammable. Potential teratogen. Health hazard when inhaled. buffer (imidazole) and solvent (methanol. buffer (imidazole). oxidant Ignition temp. xylene or trichloroethaylene). Ignition temp. 13. Skin irritant. Ignition temp. Keep away from open flames or sparks.1 One-component reagent Composition: sulfur dioxide. Health hazard when inhaled. sulfur dioxide. Disposal: as an organic solvent.1 ppm. 2methoxyethanol or diethyleneglycolmonomethylether). 13. swallowed or allowed to contact skin. 2methoxyethanol or diethyleneglycolmonomethylether). Keep away from open flames or sparks.: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: . iodine. Irritant when inhaled. buffer (imidazole) and solvent (methanol. 2-methoxyethanol.3 Reagents for coulometry: Composition: iodine. Keep container tightly closed and far removed from open flames or sparks.: 87 °C Ignition temp. Do not let reagent contact skin or eyes. Safety: flammable to extremely flammable. Ignition temp. chloroform. and solvent (methanol. The KF solvent contains: sulfur dioxide. poisonous when inhaled or swallowed. tetrachloromethane.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. 2-methoxyethanol). Disposal: as an organic solvent. swallowed or allowed to contact skin. Health hazard when inhaled. Poisonous when inhaled or swallowed.

: 6°C MAK value: 20 ppm Extremely flammable.: 95 °C Irritant for skin and eyes. Health hazard upon inhalation 98 . Ignition temp. Ignition temp. Ignition temp. Irreversible damage possible. Potential teratogen.: inflammable MAK value: 20 ppm Irritant for skin and eyes.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.

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Evaluation of the appropriate titration system (DQ) i. Switzerland Tel.com For more information Mettler-Toledo AG. Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. ©09/2009 Mettler-Toledo AG Printed in Switzerland. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. ME-51725145A Markt Support AnaChem . The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments. Routine operation including PQ. www. evaluation. specification of the analytical requirements and purchase decision 2. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. method validation.mt.e. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. development of SOPs and maintenance of the validated state of the analytical system.

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